Fuel oil composition



United States Patent 3,089,761 FUEL OIL COMPOSITION Harry J. Andress,Jr., Pitman, N.J., assignor to Socony Mobil Oil Company, Inc., acorporation of New York No Drawing. Filed May 16, 1958, Ser. No. 735,680

" 15 Claims. (Cl. 44-63) This invention has to do with improved fuel oilcompositions. More specifically it has to do with fuel oils which havebeen stabilized and which are particularly suitable for use asindustrial and domestic fuels.

This application is a continuation-in-part of my application Serial No.661,291, filed May 24, 1957, which, in turn, is a continuation-in-partof my earlier application Serial No. 596,460, filed July 9, 1956. Thetwo applications have been abandoned.

The fuel oils improved in accordance with this invention are hydrocarbonfractions having initial boiling points of at least about 100 F. and endpoints not higher than about 750 F., and which boil substantiallycontinuously throughout their distillation ranges. Such fuel oils aregenerally known as distillate fuel oils. It is to be understood,however, that this term is not restricted to straight-run distillatefractions. Thus, as is well known to those skilled in the art, thedistillate fuel oils can be -straight-run distillate fuel oils,catalytically or thermally tively low viscosities, pour points and thelike. The principal property which characterizes the contemplatedhydrocarbon fractions, however, is the distillation range. As mentionedhereinbefore, this range will lie between about 100 F. and about 750 F.Obviously, the distillation range of each individual fuel oil will covera narrower range falling, nevertheless, within the above-specifiedlimits. Likewise, each fuel oil will boil substantially, continuouslythroughout its distillation range.

The fuel oils particularly contemplated herein are Nos. 1, 2 and 3 fueloils used in domestic heating and as diesel fuel oils, particularlythose made up chiefly or entirely of cracked distillate stocks. Thedomestic heating oils generally conform to the specification set forthin ASTM Specifications D396-48T; the boiling characteristics are such asthe following: ten percent evaporation at a maximum temperature of 350F.440 F.; ninety (90) percent evaporation at a maximum temperatureranging from 450 to 675 F. The specifications for diesel fuels aredefined as ASTM Specifications D975-48T; the boiling characteristics areillustrated by: ninety (90) percent evaporation at a maximum temperaturevarying from about 550 F. to about 675 F. and an end point varying fromabout 575 F. to about 725 F.

contemplated herein also are fuels for jet combustion engines, alsoreferred to as aviation turbines. Typical jet fuels are defined inMilitary Specification MIL-P 5624B. For example, such fuels can have: aninitial boiling point of 250 F., a ten (10) percent evaporation at 410F., fifty (50) percent at 425 F., ninety (90) percent at 500 F., and endpoint of 572 F. In general, jet fuels contain hydrocarbons boiling inthe gasoline and fuel oil ranges, with the major proportion being in thelatter range.

In recent years, fuel oils of the foregoing character have beensubjected to relatively mild hydrogenation treatments in order toimprove them in one or more properties. Sulfur-content is generallyreduced, so too is phenol and nitrogen contents. Typical of such mildhydrogena- 3,089,761 Patented May 14, 1963 tion treatments, generallydesignated in the art as hydrofining" of fuels, is that described by H.Hoog in US. Pat- But No. 2,608,521, issued August 26, 1952. Advantageousmild hydrogenation procedures are described by F. I. Ciapetta et al. inSerial No. 360,662, filed June 10, 1953. By way of illustration, a fueloil can be mildly hydrogenated in the presence of a cobalt molybdatecatalyst under conditions including: a temperature of 600- 750" F.;hydrogen pressure of 200-1000 pounds per square inch; hydrogen recycleof 1000 cubic feet per barrel of oil; hydrogen consumption of -250 cubicfeet per barrel of oil.

As is well known in the art, fuel oils of the abovedefined characterhave a tendency to deteriorate in storage and to form colored bodies andsludge therein. It is to be recognized that such undesirable featuresare less pronounced with hydrofined fuel oils than with fuel oils not sotreated; however, hydrofined oils are less responsive to agents added toreduce sediment formation and/ or screenclogging, and other agents addedto inhibit rust formation. This deterioration of the oil is highlyundesirable in that it causes serious adverse effects on thecharacteristics of the oil, particularly on the ignition and burningqualities thereof. It is also a contributory factor, along with thepresence of other impurities in the oil, such as rust, dirt andmoisture, in causing clogging of the equipment parts, such as screens,filters, nozzles, etc., as is explained hereinbelow. An importanteconomical factor is -also involved in the problem of oil deteriorationin storage, viz., customer resistance. Thus, customers judge the qualityof an oil by its color and they oftentimes refuse to purchase highlycolored oils. It will be appreciated, then, that since fuel oils ofnecessity are generally subject to considerable periods of storage priorto use, the provision of a practical means for preventing thedeterioration of the fuel oil during such storage would be a highlydesirable and important. contribution to the art.

Another and distinct problem that has plagued fuel oil manufacturers andusers is that referred to as screenclogging. This involves thedeposition of foreign substances, such as water droplets, rust and dirtparticles, as

well as any sludge material formed by the deterioration of the oil, onthe metallic surfaces of screens and filters of burners and engines inwhich the oil is utilized. Additives have been developed to impartanti-clogging properties to fuel oils, functioning therein to inhibitthe aforesaid deposition of foreign substances. The mechanism by whichthe clogging is prevented involves the adsorption of the anti-cloggingagent or additive on the metal surfaces whereby the contacting of thesesurfaces by the foreign substances and/or preformed sludge is prevented.In this way, deposition and build-up of these materials on the metalsurfaces is avoided. -It will be appreciated, therefore, that theproblem of preventing screen-clogging by fuel oils is entirely differentfrom that of preventing the formation of sediment and color therein asoccurs in the oil during prolonged periods of storage. Thus, it will beappreciated that any fuel distribution system will contain small amountsof foreign substances, such as condensed moisture and particles of rustand dirt, which become entrained in the oil, even though the oil has notbeen stored for any appreciable length of time. On the other hand, fueloils which have been in storage for substantial periods of time willalso contain another kind of sediment, or sludge, which is produced bythe gradual deterioration of the oil per so. This sediment, or sludge,is formed in the oil as the result of chemical phenomena. Thus, duringstorage, oxidation of the various components of the oil, such aspyrrolic compounds; phenols and thiophenols present therein, takes placeforming quinoid molecules which condense with one another and/ or withother active hydrogen compounds also present in the oil to producehighly colored bodies of increasing molecular weight. When an oil hasbeen in storage for any substantial period of time these compoundsseparate out as insoluble sludge. Additives have also been developed toinhibit the formation of sediment or sludge in the oil due to oxidativedeterioration of the oil in storage, as above described. Such additivesact by inhibiting the initial oxidation and the subsequent reactionswhich produce such sludge.

It is apparent, then, that the problem of preventing screen-clogging byfuel oils is entirely different from the problem of preventing theformation of sediment and color therein as occurs in the oil duringprolonged periods of storage. As evidence of the difference betweenthese problems, additives which prevent screen-clogging will notnecessarily have any effectiveness in preventing the formation ofsediment and color. correspondingly, other additives which effectivelyinhibit sediment and color formation do not necessarily have anti-screenclogging properties.

Another serious problem encountered with fuel oils is their tendency toemulsify when in contact with relatively small amounts of water. Duringstorage and trans portation of fuel oils, water often gets into storagetanks, pipelines, tankers, and like storage equipment. Then, when thefuel oils are to be used, equipment dilficulties and/or ignition failureresult from the emulsions formed of the fuel and water. This problembecomes more severe when certain additives are present in the oils, theadditives serving to improve the oils in one or more properties butserving to increase the emulsification tendencies of the oils. .This isdemonstrated hereinafter by representative test results.

It is the object of this invention to stabilize fuel oils.

It is a further object of the invention to provide fuel oils stabilizedagainst the formation of sediment therein.

Still another object of the invention is to provide a fuel oil free fromscreen-clogging tendencies.

An important object of the invention is to provide a fuel oil stabilizedagainst the formation of sediment and color and also free fromscreen-clogging tendencies.

A still further object of the invention is to provide a fuel oil havingexcellent anti-rust properties.

A primary object of the invention is to provide a fuel oil improved asindicated by the foregoing objects and further improved by having littleor no tendency to emulsify when in contact with small amounts of water.

Additional objects of the invention will be apparent wherein: R is analkylene group having either 2 or 3 carbon atoms; R is hydrogen or analiphatic group preferably an aliphatic group having from about 8 toabout 18 carbon atoms; and n is an integer of at least 2 and preferably2 to 4 when R has 2 carbon atoms, and n is an integer of at least 1 andpreferably 2 to 4 when R has 3 carbon atoms, there being no upper limitto the number of alkylene groups in the molecule.

As indicated by the foregoing general formula, the aliphatic polyaminescontemplated herein include polyethylene polyamines. Typical of suchcompounds are diethylene triamine, triethylene tetramine, tetraethylenepentamine and pentaethylene hexamine. Of such polyamines, it has beenfound that diethylene triamine is particularly advantageous herein andrepresents a preferred reactant.

Included also among the polyamines of the foregoing general formula arepropylene polyamines. Of such polyamines, preferred are thosecharacterized by one primary amino group and one secondary amino group,the said amino groups being linked to different terminal carbon atoms ofa normal propyl group. Representative of such amines are propylenediamine and iminobis propyl amine (i.e., dipropylene triamine).

Particularly outstanding of the propylene diamines are N-substitutedpropylene diamines wherein the substituent group contains from about 8to about 18 carbon atoms. A number of mixtures of such diamines arepresently available commercially. The diamines of the mixtures arerepresented structurally by RNHCH CH CH NH wherein R is aliphatic innature, and varies from about 8 to about 18 carbon atoms. One suchmixture, identified herein as A, is one wherein about 10% of the Rgroups are hexadecyl, about 10% are octadecyl, about 35% areoctadecenyl, and about 45% are octadecadienyl. Another mixture is 8"; inthis product about 8% of the R groups are octyl, about 9% are decyl,about 47% are dodecyl, about 18% are tetradecyl, about 8% are hexadecyl,about 5% are octadecyl and about 5% are octadccenyl. A third mixture isC, in which about 30% of the R group are hexadecyl, about 25% areoctadecyl and about 45 are octadecenyl. Of such mixtures, mixture A isparticularly preferred herein.

Reacted with the polyamines described above are naphthenic acids whichare monocarboxylic acids obtained from crude petroleum or fromdistillates thereof. Suchacids are well known in the art, having beenwell described in the Encyclopedia of Chemical Technology, edited by R.F. Kirk et al.; The lnterscience Encyclopedia, Inc., New York, 1952,volume 9, pages 241-247; and by Carleton Ellis in The Chemistry ofPetroleum Derivatives, The Chemical Catalog Co., Inc.; New York, 1934;chapter 48. Earlier it had been considered that all naphthenic acidscould be used for reaction with the aforementioned alkylene polyaminesto form satisfactory products. However, it has been discovered that onlycertain naphthenic acids are suitable. The naphthenic acids which formreaction products capable of inhibiting emulsion formation in a fueloil, are those having molecular weights up to about 300. Thiscorresponds to an acid number above about 180, and an average of up toabout 19 carbon atoms per molecule. Excellent results have been obtainedwith a naphthenic acid having an acid number of about 200, an averagemolecular weight of 275-300, and a major proportion thereof having from15 to 19 carbon atoms per molecule. Naphthenic acids availablecommercially to date are mixtures rather than individual compounds.

The reaction products of this invention are prepared by reaction of fromabout 2 to about 4 molar proportions of a naphthenic acid with one molarproportion of an alkylene polyamine of the character described abovewherein R' is hydrogen or is an aliphatic group having less than about 7carbon atoms; a preferred ratio is 2:1. Contemplated herein also arereaction products obtained by reaction of from about 1 to about 2 molarproportions of a naphthenic acid with one molar proportion of of analkylene polyamine represented by the general formula, wherein R has atleast about 8 carbon atoms; the preferred ratio for preparing suchproducts is 111.

Products formed by reacting one molar proportion of a naphthenic acidwith one molar proportion of an alkylene polyamine wherein R is hydrogenor an aliphatic group of about 7 carbons or less, are not completelysoluble in fuel oil and do not act as sediment inhibitors therein.Products prepared by reacting more than two molar proportions ofnaphthenic acid with one molar proportion of an alkylene polyaminehaving an R group of hydrogen or an aliphatic group of about C, or less,are less effective sediment inhibitors and anti-screen-clogging agents,than are those products obtained by using a molar ratio of 2:1. Productsprepared by reacting more than one molar proportion of naphthenic acidwith one molar proportion of an alkylene polyamine having an R group ofC, or greater, are likewise less effective than zlare1 those productsobtained by using a molar ratio of when the alkylene polyamine used is apolyethylene polyamine such as diethylene triamine, and two molarproportions of a naphthenic acid are reacted with one molar proportionof said amine, the reaction product so obtained, most probably, ispredominantly comprised of one1 or more imidazolines represented by thegeneral formu a:

HIC CHI II wherein R" is naphthenyl.

When the alkylene polyamine is a polypropylene polyamine such asdipropylene triamine, and two molar proportions of naphthenic acid arereacted with one molar proportion of the amine, the reaction product soobtained, most probably, is predominantly comprised of one or moretetrahydropyrimidines represented by the general formula:

wherein R" is naphthenyl.

correspondingly, when the alkylene polyamine used is a propylenepolyamine such as an N-octyl propylene diamine, and one molar proportionof naphthenic acid is reacted with one molar proportion of said diamine,the reaction product is considered to be primarily comprised of one ormore tetrahydropyrimidines of the following formula:

wherein R' is octyl and R" is naphthenyl.

It will be clear, therefore, that since available naphthenic acids aremixtures, since some of the polyamines are mixtures, and since the molarratios of the naphthenic acid and polyamines are subject to somevariations, the products are better described as reaction products thanas individual compounds. This is particularly so when mixtures ofdiamines, such as A, 13" and C" above, are used as reactants. I

The reaction products contemplated herein are used in fuel oils inconcentrations varying between about 1 pound per thousand barrels ofoil, and about 200 pounds per thousand barrels of oil. Preferably theconcentration will vary between about and 100 pounds per thousandbarrels. In terms of weight percent, based upon the weight of the fueloil, the concentrations vary preferably between about 0.005% and about0.05%.

If it is desired, the fuel oil compositions of this invention cancontain other additives for the purpose of achieving other results.Thus, for example, there can be present foam inhibitors, anti-rustagents, and ignition and burning quality improving agents. Examples ofsuch additives are silicones, dinitropropane, amylnitrate, metalsulfonates and the like. A further example of other additives which maybe used with the new fuel oil compositions are tertiary alkyl primaryamines described in 6 application Serial No. 578,881, filed April 18,1956, now Patent No. 2,947,749.

The following specific examples are set forth for the purpose ofillustrating the fuel oil compositions of this invention and for thepurpose of distinguishing them from related fuel oil compositions. Insuch examples, the reaction products formed from naphthenic acidsillustrate the invention.

TETRAHYDROPYRIMIDllNE-CONTAINING REAC- TION PRODUCTS Example I Thefollowing preparation illustrates a typical method for producing areaction product containing tetrahydropyrimidines. A mixture of 1 mole(282 parts by weight) of oleic acid and 1 mole (370 parts) of aminemixture A," described above, was refluxed in xylene solution for 4hours. The reaction mixture was then slowly heated to 235 C. and washeld at this temperature until the evolution of water ceased. Two (2)moles (36 parts) of water were collected. The final product, containing4.0 percent of nitrogen, is a mixture of 2,3-disubstitutedtetrahydropyrimidines which corresponds to the formula:

where R"=heptadecenyl and R: 10% octadecyl, 10% hexadecyl, 35%octadecenyl, and 45% octadecadtenyl.

Example 2 A mixture of 1.15 moles (350 parts) of a commercial tall oil(identified herein as mixture D") and 1.15 moles (330 parts) of aminemixture B, identified above, was refluxed in xylene solution for 4hours. The reaction mixture was then heated to 240 'C. during a periodof 6 hours. About 2.1 moles (38 parts) of water were collected.

Mixture D" is a refined tall oil having an acid number of 185 andcomprising a mixture of rosin acids and fatty acids. The fatty acidsrange from C to C The final product, containing 2.86 percent nitrogen,is a mixture of a 2,3-disubstituted tetrahydropyrimidines correspondingto the formula:

where R"=alkyl groups from tall oil (a mixture of rosin and fatty acids)and R'=a mixture of C to C alkyl groups and averaging C in molecularweight.

Example 3 A mixture of 0.28 mole parts) of a crude mixture of dimeracids (identified herein as mixture E") and 0.56 mole (200 parts) ofamine mixture C," described above, was refluxed in xylene solution for 4hours. The reaction mixture was then heated to 220 C. during a period of10 hours. One mole (18 parts) of water was collected. The crude mixtureof dimer acids'has an acid number of and comprises acids ranging from C-C The final product, containing 4.8 percent of nitrogen, is a mixtureof his 2-(3 alkyl tetrahydropyrimydyl) alkylene corresponding to theformula:

7 where R"==alkenyl group from dimer acids and R'=a mixture of 30%hexadecyl, 25% octadecyl and 45% octadecenyl.

Example 4 Example 5 A mixture of 0.5 mole (76 parts) of a 50% aqueoussolution of glycolic acid and 0.5 mole (185 parts) of amine mixture Awas stirred for 8 hours in an xylene solution. The reaction mixture wasthen heated to 200 C. during a period of 9 hours. A total of 55 parts(3.5

moles). of water was collected. The final product, containing 7.0percent of nitrogen, was a mixture of 2-hydroxy methyl, 3-alkylsubstituted tetrahydropyrimidines corresponding to the formula:

where R'=10% hexadecyl, 10% octadecyl, 35% octadecenyl and 45octadecadienyl.

Example 6 A mixture of 1.06 moles (380 parts) of naphthenic acid (acidnumber, 198) having an average molecular weight of about 280, and 1.06moles (423 parts) of amine mixture A was refluxed in xylene solution for4 hours. The reaction mixture was then slowly heated to 245 C. and washeld at this temperature until the evolution of water ceased. Two moles(36 parts) of water were collected. Xylene was also removed with thewater. The final product, containing 4.5 percent of nitrogen, is amixture of 2,3-disubstituted tetrahydropyrimidines which correspond tothe formula:

where R"=naphthenyl and R'=l0% octadecyl, 10% hexadecyl, 35% octadecenyland 45% octadecadienyl.

Example 7 Amine mixture C" was used in place of amine mixture A,following the procedure of Example 6. The final product also containsabout 4.5 percent nitrogen. The final product is a mixture of2,3-disubstituted tetrahydropyrimidines which correspond to the formula:

where R"=naphthenyl and R'=30% hexadecyl, 25% octadecyl and 45%octadecenyl.

Example 8 A mixture of 0.72 mol (200 parts) of naphthenic acid (acidnumber, 203) having an average molecular weight of about 275, and 0.72mol (288 parts) of amine mixture C was refluxed in xylene solution for 4hours. The reaction mixture was then slowly heated to 275 C. and washeld at this emperature until the evolution of water ceased. About 1.4mols (25 parts) of water were collected. The final product containsabout 4.5% nitrogen and has the same formula as shown for Example 7.

Example 9 A mixture of 0.43 mol parts) of naphthenic acid (acid number,240) having an average molecular weight of about 230, and 0.43 mol (171parts) of amine mixture A" was refluxed in xylene solution for 4 hours.The reaction mixture was then slowly heated to 275 C. and was held atthis temperature until the evolution of water ceased. About 0.86 mol (16parts) of water were collected. The final product contains about 5.2%nitrogen and has a formula similar to Example 6.

Example 10 A mixture of 0.65 mol (200 parts) of naphthenic acid (acidnumber, 178) having an average molecular weight of about 297, and 0.65mol (255 parts) of amine mixture C was refluxed in xylene solution for 4hours. The reaction mixture was then slowly heated to 275 C. and washeld at this temperature until the evolution of water ceased. About 1.2mols (22 parts) of water were collected. The final product containsabout 4.0% nitrogen and has a formula similar to Example 7.

Example 11 A mixture of 0.57 mol (200 parts) of naphthenic acid (acidnumber, 159) having an average molecular weight of about 330, and 0.57mol (228 parts) of amine mixture C was refluxed in xylene solution for 4hours. The reaction mixture was then slowly heated to 275 C. and washeld at this temperature until the evolution of water ceased. About 1.2mols (22 parts) of water were collected. The final product containsabout 3.6% nitrogen and has a formula similar to Example 7.

Example 12 A mixture of 0.51 mol (232 parts) of naphthenic acid (acidnumber 122) having an average molecular weight of about 415, and 0.51mol (202 parts) of amine mixture C was refluxed in xylene solution for 4hours. The reaction mixture was then slowly heated to 275 C. and washeld at this temperature until the evolution of water ceased. About 0.9mol (16 parts) of water were collected. The final product contains about3.1% nitrogen and has a formula similar to Example 7.

Example 13 A mixture of 0.6 mol (200 parts) of naphthenic acid (acidnumber, 159) having an average molecular weight of about 330, and 0.6mol (182 parts) of amine mixture B" were refluxed in xylene solution for4 hours. The reaction mixture was then slowly heated to 275 C. and washeld at this temperature until the evolution of water ceased. About 1.1mols (20 parts) of water were col lected. The final product containsabout 3.6% nitrogen with a formula similar to Example 7.

Example 14 A mixture of 1.06 mols (300 parts) of naphthenic acid (acidnumber, 198) having an average molecular weight of about 280, and 0.53mol (69.5 parts) of iminobispropylamine (dipropylene triamine), wererefluxed in xylene solution for 4 hours. The reaction mixture was thenslowly heated to 275 C. and was held at this temperature until water wasno longer evolved (2 hours). About 1.5 mols (27 parts) of water werecollected. The reaction product is primarily comprised of 2-naphthenyI-Z-naphthenamidopropyl tetrahydropyrimidines represented as:

HI n-omomcnmn 41" wherein R" is naphthenyl.

Example 15 A mixture of 1.0 mol (282 parts) of oleic acid and 0.5 mol(65.5 parts) of dipropylene triamine was refluxed in xylene solution for4 hours. The reaction mixture was then slowly heated to 250 C. and wasmaintained at this temperature until the evolution of water ceased.About 1.5 mols (27 parts) of water were collected. The reaction productis predominantly comprised of a 2,3-disubstituted tetrahydropyrimidinerepresented as:

0 l l Hal? N-cmomoumH R" whereih R is oleyl.

IMIDAZOLINE-CONTAINING REACTION PRODUCTS Example 16 A mixture of 1.76mols (500 parts) of naphthenic acid having an acid number of 198, and0.88 mol (91 parts) of diethylene triamine were refluxed in xylenesolution for 4 hours. The reaction mixture was then slowly heated to 275C. and was held at this temperature until the evolution of water ceased(about 2 hours). Xylene was also removed along with the water. About 2.6mols (47 parts) of water were collected. The reaction product ispredominantly comprised of l-naphthenamidoethyl 2naphthenylimidazolines, corresponding to Iho-on, 0

N N-CIIzClIsNIIiL-R" wherein R" is naphthenyl.

Example 17 A mixture of 1.76 mols (500 parts) of naphthenic acid havingan acid number of 198, and an average molecular weight of about 280, and0.88 mol (129 parts) of triethylene tetramine were relluxed in xylenesolution for 4 hours. The reaction mixture was then slowly heated to 300C. and was held at this temperature until the evolution of water ceased(about 2 hours). Again, xylene was removed with the water. About 3.2mols (57 parts) of water were collected. The reaction product ispredominantly comprised of ethylene 1,l'-bis- Z-naphthenylimidazolinesrepresented as trio-om 1noo1h N N-OIIrCIIr-N N wherein R" is naphthenyl.

Example 18 A mixture of 1.09 mols (300 parts) of naphthenic acid (acidnumber, 203) having an average molecular weight of about 275, and 0.545mol (103 parts) of tetraethylene pentamine were refluxed in xylenesolution for 4 hours. The reaction mixture was then slowly heated to 275C. and was held at this temperature until water was no longer evolved(about 2 hours). About 1.7 mols (3l parts) of water were collected. Thereaction product is primarily comprised ofl-naphthenamidotriethylenediimino-2-naphthenyl imidazolines representedas wherein R" is naphthenyl.

Example 19 A mixture of one mol (282 parts) of oleic acid and 0.5 mol(73 parts) of triethylene tetramine were refluxed in xylene solution for4 hours. The reaction mixture was then slowly heated to 275 C. and washeld at this temperature until the evolution of water ceased. About 1.94mols (35 parts) of water were collected. The reaction product isprimarily ethylene, l,l'-bis-2- octadecenyl imidazoline, represented asH1O CIT; 1120 CH1 N l l R wherein R" is octadecenyl.

Example 21 A mixture of 0.5 mol parts) of linoleic acid and 0.25 mol(36.5 parts) of triethylene tetramine were refluxed in xylene solutionfor 4 hours. The reaction mixture was then slowly heated to 275 C. andwas held at this temperature until the evolution of water ceased. Aboutone mol (18 parts) of water were collected. The reaction product isprimarily ethylene l,l-bis-2-octadecadienyl imidazoline represented byII1C-CII:

wherein R" is octadecadienyl.

Example 22 A mixture of 0.5 mol (128 parts) of palmitic acid and 0.25mol (36.5 parts) of triethylene tetramine were refiuxed in xylenesolution for 4 hours. The reaction mixture was then slowly heated to 275C. and was held at this temperature until the evolution of water ceased.About one mol (18 parts) of water were collected. The

ill

wherein R" is hexadecyl.

Example 23 A mixture of 0.5 mol (114 parts) of myristic acid and 0.25mol (36.5 parts) of triethylene tetramine were refluxed in xylenesolution for 4 hours. The reaction mixture was then slowly heated to 275C. and was held at this temperature until the evolution of water ceased.About one mol (18 parts) of water were collected. The reaction productis primarily ethylene l,l'-bis-2-tetradecyl imidazoline represented asH1CCH: HzC-CH N N-OHICHr-N N wherein R" is tetradecyl.

Ex mple 24 A mixture of 0.5 mol (100 parts) of lauric acid and 0.25 mol(36.5 parts) of triethylene tetramine were refluxed in xylene solutionfor 4 hours. The reaction mixture was then slowly heated to 275 C. andwas held at this temperature until the evolution of water ceased. Aboutone mol (18 parts) of water were collected. The reaction product isprimarily ethylene l,l'-bis-2-dodecyl imidazoline represented as whereinR" is lauryl, primarily dodecyl.

Example 25 A mixture of 1.5 mol (25.8 parts) of normal capric acid and0.75 mol (77.2 parts) of diethylene triamine were refluxed in xylenesolution for 4 hours. The reaction mixture was then slowly heated to 275C. and was held at this temperature until the evolutionof water ceased.About 2.5 mols (45 parts) of water were collected. The reaction productis primarily 1-n-decylamidoethyl-Z-n-decyl imidazoline represented aswherein R is n-decyl.

Example 26 A mixture of 0.92 mol (300 parts) of a commercial abieticacid having an acid number of 170 and 0.46 mol (47 parts) of diethylenetriamine, were refluxed in xylene solution for 4 hours. The reactionmixture was then slowly heated to 275 C. and was held at thistemperature until the evolution of water ceased. About 1.5 mols (27parts) of water were collected. The reaction product is predominantlycomprised of a mixture of 1- abietyl amidoethyl-Z-abietyl imidaaolinesrepresented as wherein R" is abietyl.

The effectiveness of the additives of this invention and of relatedproducts in stabilizing a typical fuel oil against sediment formationtherein, is shown by screenwlogging test data. The amount ofscreen-clogging is determined with a Sundstrand V3 or 81 home fuel oilburner pump having a self-contained, l00-mesh Monel metal screen. About0.05 percent, by weight, of a naturally-formed fuel oil sludge, composedof fuel oil, water, dirt, rust, and organic sediment, is added to tenliters of the fuel oil under test. This mixture is circulated by thepump through the screen for six hours. Then the sludge deposited on thescreen is washed off with normal pentane, and filtered through a taredasbestos (Gooch crucible) filter. After it is dried, the material on thefilter is washed with a 5050 (volume acetone-methanol mixture. The totalamount of organic sediment is determined by evaporating the n-pentaneand the acetone-methanol filtrates, and weighing the residue. materialon the filter is the amount of inorganic sediment deposited. The sum ofthe weights of the organic and the inorganic deposits, in milligrams,gives the weight of sludge deposited, which weight is compared with theweight of sludge deposited from the uninhibited (blank) fuel oil todetermine the percent of screenclogging. The uninhibited fuel oil, aftersix hours on test, effects percent screen-clogging. Thus, the comparisonpercentagewise between the weight of sludge deposited by the uninhibitedfuel oil and the inhibited fuel oil affords a measure of the percent ofscreen-clogging. The fuel oil used in the test is a blend comprisingsixty percent (by weight) of catalytically cracked component and 40% ofstraight-run component, the blend having a boiling range from about 320F. to about 640 F. The data obtained from said tests are provided inTable I.

TABLE I Cone. lbs .(JLOOO b Is.

Screen clogging. percent Product ot-Examplc, acid, umlno As indicatedabove, the naphtlhenyl-substituted reaction products of this inventionare also effective in inhibiting screen-clogging of hydrofined fueloils. Tests corresponding to those described in connection with Table Iwere carried out with a hydrofined fuel oil having a boiling range fromabout 320 F. to about 640 F. Data obtained in such tests are shown inTable II.

The weight of the A demonstration of the sediment inhibiting characterof the additives contemplated herein and of related products is shown byresults of 110 F. storage tests. In this test, a SOO-rnilliliter sampleof the fuel oil under test is placed in a convected oven maintained at110 F. for a period of twelve weeks. Then, the sample is removed fromthe oven and is cooled. The cool sample is filtered through a taredasbestos filter (Gooch crucible) to remove the insoluble matter. Theweight of such matter, in milligrams, is reported as the amount ofsediment.

,In this test, a sample of the blank, uninhibited oil is run along withthe fuel oil blend under test. The oil used is the same as thatdescribed above in connection with Table I. The effectiveness of a fueloil composition containing an inhibitor is determined by comparing thetest data therefor with the test data for the uninhibited, blank oil.Results of the storage tests are given in Table III.

Table III Product of-Example, acid, amine Cone. lbs./ Sediment,

1,000 hbis. mgJllter (Uninlilblted fuel oil blend) 80 (1) Olelc, A" 50 0(Unlnhlbitcd fuel oil blend) 0 85 (2) D 100 S (Unlnhlblted fuel oilblend 0 110 (J) E C 100 10 (Uninhlbited fuel oil blend). 0 8S (4) Glythis, A 50 4 (Uninhibltcd fuel oil blend). 0 149 5) Glscollc, "A" 100(Uninhibited fuel oil blend). 0 08 (b) Nuphthenic, 50 6 (Unlnhlbltedfuel oil blend 0 05 (7) Nnphthenic, "C" 100 7 (Unmblbltcd fuel oilblend)... 0 24 (14) Naphtlicnlc, dlpropylone trlamine 50 7 (Uninhibitedfuel oil blend) 0 77 (15) Olele, dlpropylcnc trlamine.- 5O 14(Unlnhlbited fuel oil blend) 0 8 (l6) Napththcnlo, diethylcne trimnlno50 7 EUnlnhihited fuel oil blend) 0 24 17) Nuphthenlc, trlethylenetetram 50 (i (Unlnhiblted fuel oil blend) 0 1'20 18) Naphthenlc,tetraetbylene pcntomine. 50 45 Sedimentation tests have also beencarried out with an unstable, West Coast diesel fuel. percentevaporation of 600 F. and an end point of 700 F. In the sedimentationtest, described in connection with the data of Table III above, theuninhibited fuel formed 118 milligrams per liter. When a concentrationof 100 pounds per M/bbls. of the product of Example 7 (naphthenicAcid-Mixture "C) was used in the fuel, the sediment value was only 20milligrams.

Additional sedimentation tests of the same nature were made with theproducts of this invention, the base fuels being hydrofined fuel oilshaving boiling ranges from about 320 F. to about 640 F. Results of thesetests are given in Table IV, following.

This fuel had a 90 TABLE IV Product ofExample, acid, nnnlne Cone. 1hs./Sediment,

1000 bbls. mgs./lltcr Unlnhlblted fuel oil) 0 13 6) Nnphthenlc, A 10 90) Nnphtheulc, A.- 25 7 (0) Nnphthenlc, "A".- 50 7 (Unlnlliblted fuel0ll)-- 0 10 (7) Naphtbenlc, 0",- 10 3 (7) Naphthcnlc, C.. 5 4 (7)Nuphthenlc, C".. 3 (Unlnhiblted fuel oil) 0 10 (i6) Nnphthenlc,dlethylene trinmlne 25 4 16) Naphthenlc, dlethylenc trlamine 50 3 Asmentioned hereinabove, the additives of this invention are alsoexcellent anti-rust agents. This is shown by results obtained byconducting A.S.T.M. Rust Test D-665 with the blank fuel oil blend andwith the latter containing small amounts of typical additives of thisinven- As indicated hereinabove, emulsion-forming tendencies of fueloils containing certain additives militate against their use. Whilecertain of the reaction products shown above, those not formed fromnaphthenic acids having molecular weights up to about 300 are effectivesediment inhibitors and anti-screen-clogging agents, they do not inhibitemulsion formation. In fact, in some cases, the reaction productspromote emulsion formation. In contrast, the related products preparedfrom naphthenic acids having molecular weights up to about 300 inhibitemulsification. This is demonstrated by the following test and testresults.

The procedure for the fuel oil emulsion test is as follows: a 200milliliter portion of the fuel to be tested and 20 milliliters ofdistilled water are placed in a clear glass pint bottle. The bottle istightly capped and set in an Everbach mechanical shaker in a horizontalposition such that the maximum degree of agitation is afforded. Theshaker is run at its maximum setting for 5 minutes. The bottle is thenremoved and allowed to stand in an upright position in the dark for 24hours. At the end of the 24 hour settling period, the appearance of thewater layer is noted. The fuel layer is siphoned off, care being takennot to disturb the oil-water interface, and is discarded. A freshportion of the fuel oil being tested is then added. The describedsequence of steps is repeated. If no emulsion appears in the water layerafter this sequence has been performed ten times, the oil is consideredto have passed the test. On the other hand, if, after any 24 hoursettling period in the procedure, there is any degree of emulsificationin the water layer, the fuel is considered to have failed the test. Thistest procedure has been found to provide emulsions in inhibited oilssimilar to emulsions which occur in these same oils only after prolongedperiods of normal handling and storage in the field on a commercialbasis.

The fuel oil used in the emulsion tests is a blend comprising percent ofcatalytically cracked component and ing range (approximate) of 320-640F. Results of the emulsion tests are shown in Tables VI and VII. InTable VI, distinction is drawn between products obtained from suitablenaphthenic acids and acids of other types. In Table VII, distinction isdrawn between naphthenic acids differing in molecular weight.

TABLE VL-FUEL OIL EMULSION FORMATION TEST Cone, Emulsion Inhibitor,acid, amine lbs/1,000 results bbls.

Uninhiblted Fuel Pass. Ex. 6, Naphthenlc, "A".. Do. Do 25 Do. Do 50 Do.Ex. 7, Nnphthenic, C" 10 Do. Do 25 Do. Do 50 Do. Ex. 14, naphthentc,dlpropylcne trlnmlne 25 Do. Ex. 15, oleic, dipropyiene triamlne 10 Fall.

Do 25 Do. Do 50 Do. Ex. 16, naphthenic, diethyleue triamlne.- 25 Puss.

Do 50 Do. Do 100 Do. Ex. 11, naphthenlc, trlethylene tetramlne 25 Do. Do50 Do. Ex. 18, nuphthenic, tetraethylene pcntarnlne" 25 D0. Ex. 19,steurlc, triethylene tetramine- 25 Fail. Ex 20, c,trletl1ylenetetrumine.. 25 Do. Ex 21 llnoleic, trlethylene tetramine 25Do. Ex 22, palmlttc, trlethylene tetrnmlne- 25 D0. Ex 23, myrlstlc,triethylene tetramine--- 25 Do. Ex 24, laurlc, triethylene tetramiue..25 Do. -Ex 25, capric, dlethylene trlamine.-- 25 Do. Ex 26, abietic,dlethylenetrinmine 25 D0.

TABLE VII.FUEL OIL EMULSION TEST Avg. moi, Cone., Inhibitor weight ofAmine lbs./ 1,000 Emulsion naph thenic bbls. results acid Unlnhibltedfuel 0 P058- Exampl 280 "A" 10 D0. D0 280 A" 25 D0. D0 280 A" 50 D0.Example 7.. 280 "C" 10 Do. Do 280 0" 25 D0. D0. 280 "C" 50 Do. Example 8275 "C" 25 Do. Do.... 275 "C" 50 D0. Example 9.. 230 "A" 25 Do. Do 230"A 50 Do. Example 10. 297 0" 25 Do. Do 297 "C" 50 D0. Example 11- 330 "C25 Full.

330 0" 50 Do. 415 "C" 25 Do.

330 13" 25 Do. 330 "B" 50 D0.

From inspection of the data provided in Table VI, it is seen that onlythe products formed from naphthenic acids pass this emulsification testand that all other closelyrelatcd products fail in this test. Thus, thelatter products are not attractive commercially for use in fuel oils,despite their behavior as anti-screen-clogging agents and sedimentinhibitors. For example, Example 15 (oleic aciddipropylenc triamine)failed immediately in this test, emulsion being formed as soon as thefuel containing the product came in contact with water. Correspondingfailures occurred with the fuels containing the products of Examples 19through 25, inclusive.

In Table VII, it is shown that reaction products, formed from naphthenicacids having molecular weights ranging from about 230 to about 297 aresatisfactory; whereas, those formed from similar acids having molecularweights from about 330 to about 415 are unsatisfactory.

In Table VII, it is shown that reaction products, formed from naphthenicacids having molecular weights ranging from about 230 to about 297 aresatisfactory; whereas, those formed from similar acids having molecularweights from about 330 to about 415 are unsatisfactory.

Additional emulsification tests were carried out with a hydrofined fueloil. The only difference between these 1 6 tests and those carried outin regard to Table VI, was the substitution of a hydrofined fuel oil forthe regular fuel oil. The hydrofined fuel oil had a range ofapproximately 320640 F. Results of such tests are shown in Table VIII.

TABLE VIIL-FUEL OIL EMULSION FORMATION TEST Inhibitor Acid AmineConc.,ibs./ Emull, is. sion results Urfilnlhlblted 0 Pass.

Exnmplefi Naphthenlc- "A" 10 Do. Do do "A" 25 Do. Do o "A" 50 D0.

Example 7. do 0" 10 Do.

0 .......Ll0 C" 25 D0.

D0 d0 0" 50 Do.

Example 16 ..do Dlethylene tri- 25 Do.

amine.

Do do (l0 50 Do.

Do do do Do.

Example 17 ..do Triethylene tet- 25 Do.

I ramiue.

Although the present invention has been described in conjunction withpreferred embodiments, it is to be understood that modifications andvariations may be resorted to, without departing from the spirit andscope of this invention. Such variations and modifications areconsidered to be within the scope and purview of the appended claims.

I claim:

1. A distillate fuel oil containing a small amount, sufficient toinhibit emulsification of the fuel oil with water, of a fueI-oil-solublecompound selected from the group represented by the general formulae:

wherein R' is selected from the group consisting of hydrogen and analiphatic group having up to 18 carbon atoms and up to two double bonds,R" is an unsubstituted naphthenyl group having a molecular weightup toabout 300, and n is selected from zero and a small whole numher.

2. A distillate fuel oil as defined by claim 1, wherein the naphthenicacid has a molecular weight from about 275 to about 300.

3. A distillate fuel oil as defined by claim 1, wherein the distillatefuel oil is a domestic heating fuel oil.

4. A distillate fuel oil as defined by claim 1, wherein the distillatefuel oil is a diesel fuel oil.

5. A distillate fuel oil as defined by claim 1, wherein the distillatefuel oil is a jet fuel.

6. A distillate fuel oil as defined by claim 1, wherein the distillatefuel oil is a hydrofined fuel oil.

7. A distillate fuel oil as defined by claim 1, wherein the distillatefuel oil is a diesel fuel oil and the compound is present in an amountbetween about 0.005 percent and about 0.05 percent by weight.

8. A distillate fuel oil containing a small amount, sufficient toinhibit emulsification of the fuel oil with water, of a fuel-oil solublecompound represented by:

wherein R is selected from the group consisting of hydrogen and analiphatic group having up to 18 carbon atoms and up to two double bonds,R" is an unsubstituted naphthenyl group having a molecular weight up toabout 300, and n is selected from zero and a small whole numher.

9. A distillate fuel oil containing a small amount, sulfi' cient toinhibit emulsification of the fuel oil with water, of a fuel-oil-solublecompound represented by the formula wherein R" is an unsubstitutednaphthenyl group having a molecular weight up to about 300.

10. A distillate fuel oil containing a small amount; sufiicient toinhibit emulsification of the fuel oil with water, of a fuel-oil-solublecompound represented by the general formula wherein R is selected fromthe group consisting of hydrogen and an aliphatic group having up to 18carbon atoms and up to two double bonds, and R" is an unsubstitutednaphthenyl group having a molecular weight up to about 300.

11. A distillate fuel oil containing a small amount, willcient toinhibit emulsification of the fuel oil with water, of a fuel-oil-solublecompound represented by the formula wherein R is a mixture of aliphaticgroups of which about 30 percent are hexadecyl, about 25 percent areoctadecyl and about 45 percent are octadecenyl, and R" is anunsubstituted naphthenyl group having a molecular weight up to about300.

12. A distillate fuel oil containing a small amount, suflicient toinhibit emulsification ofthe fuel oil with water,

II:C-CII 0 r i N N-CHIGIIiNH R" wherein R" is an unsubstitutednaphthenyl 'group having a molecular weight up to about 300.

14. A distillate fuel oil containing a small amount, sufiicient toinhibit emulsification of the fuel oil with water, of a fuel-oil-solublecompound represented by the formula moori| o N N-mm-(NIICrHmNHd-n"wherein R" is an unsubstituted naphthenyl group having a molecularweight up to about 300.

15. A distillate fuel oil containing a small amount, sutficient toinhibit emulsification of the fuel oil with water, of a fuel-oil-solublecompound represented by the formula II|C-GH| HIC CHQ N\ N-CaIh-N N I")!l il'l wherein R" is an unsubstituted naphthenyl group having amolecular weight up to about 300.

References Cited in the: file of this patent UNITED STATES PATENTS2,568,876 White et al Sept. 25, 1951 2,622,018 White et al. Dec. 16,1952 2,819,284 Shen Jan. 7, 1958 2,844,446 Cyba et al. July 22, 19582,888,337 Chenicek May 26, 1959 2,907,646 OKelly et al. Oct. 6, 19592,917,376 Stromberg et al Dec. 15, 1959 OTHER REFERENCES Surface ActiveAgents and Detergents, volume 11, by Schwartz et al., IntersciencePlllb. Inc., N.Y., 1958, pages 197 and 710.

1. A DISTILLATE FUEL OIL CONTAINING A SMALL AMOUNT, SUFFICIENT TO INHIBTEMULSIFICATION OF THE FUEL OIL WITH WATER, OF A FUEL-OIL-SOLUBLECOMPOUND SELECTED FROM THE GROUP REPRESENTED BY THE GENERAL FORMULATAE: